Volumetric Properties of Ternary-Pseudobinary Mixtures Containing Benzene and Cyclohexane

Densities have been measured as a function of composition for ternary-pseudobinary mixtures of [(benzene + toluene or methylcyclohexane) + (cyclohexane + toluene or methylcyclohexane)] by means of a vibrating-tube densimeter at atmospheric pressure and the temperature 298.15 K. The excess molar volumes, V_m^E, were calculated from the densities and correlated using the Redlich–Kister equation to estimate the coefficients and standard errors. The experimental and calculated quantities are used to discuss the mixing behavior of the components. The results show the third component, toluene and methylcyclohexane, influences the interaction between benzene and cyclohexane.     

一种新型交替迭代算法用于农药GC-MS信号快速分析

化学计量学算法为重叠GC-MS信号解析提供了有效手段. 免疫算法(IAs)可根据标准样品的信号(色谱或质谱)对重叠GC-MS信号进行解析并得到重叠信号中各组分的信息. 但是标样信号与实际测量信号之间的差别会造成解析结果出现偏差. 针对标样信号与测量信号不一致的问题, 作者提出了一种交替迭代算法用于重叠GC-MS测量信号的直接解析. 该方法在不提供标样信号的情况下可以解析出组分的质谱和色谱信息. 计算过程中, 采用随机产生的质谱作为初始输入, 利用最小二乘和IA算法交替计算质谱和色谱, 直到满足终止条件. 采用所建立的方法对40种组分的农药混合物进行了分析, 使用快速升温程序在10 min保留时间内得到了全部组分的色谱和质谱信息.     

浓度加和模型在化学混合物毒性评估中的应用

化学污染物总是以混合物形式存在于实际环境体系中. 化学混合物的毒性评估与预测是环境化学领域当前的研究热点与难题. 要评估与预测一个化学混合物的毒性效应, 首先要证明其是否具有加和性. 目前有3个加和参考模型即浓度加和模型(CA)、独立作用模型(IA)与效应相加模型(ES)用于化学混合物毒性的加和性检验. 如果混合物效应明显偏离加和参考模型预测效应, 则认为该混合物产生毒性相互作用, 即协同或拮抗. 选择不同的加和参考模型可能得出不同的相互作用结论. ES模型最早广泛应用, 但不能解释由同一化合物构成的所谓虚拟组合现象, 应用已开始受到限制. IA模型被认为适用于具有相异作用模式的化学物构成的混合物, 而CA模型适用于相似作用模式化学物构成的混合物并能合理解释ES模型不能解释的虚拟组合现象, 常常认为是化学混合物毒性预测的标准模型. 然而, 由于CA模型目前没有坚实的理论支持, 也不能直接联系混合物毒性作用机理, 同时在浓度-效应曲线的部分区域存在不能预测的所谓“预测盲区”, 因此, CA模型也只是一个工作模型, 需谨慎使用.     

Volumetric behaviour of the (2,2,4-trimethylpentane + methylbenzene + butan-1-ol) ternary system and its binary sub-systems within the temperature range (298.15–328.15) K

Densities and speeds of sound of the (2,2,4-trimethylpentane + methylbenzene + butan-1-ol) ternary system as well as all its binary sub-systems were measured at four temperatures, namely 298.15 K, 308.15 K, 318.15 K, and 328.15 K at atmospheric pressure by a vibrating-tube densimeter DSA 5000. The binary (isooctane + toluene) system was studied previously. Excess quantities (molar volume, adiabatic compressibility, and isobaric thermal expansivity) of the mixtures studied were calculated from the experimental densities and speed of sounds. The excess molar volume data were correlated using the Redlich–Kister equation. Both the positive and S-shaped excess molar volume curves were found for the systems studied. The excess molar volumes versus concentration of binary systems differed in the shape and temperature dependence. The experimental binary data were compared with literature data. The experimental excess molar volumes were analyzed by means of the Extended Real Associated Solution (ERAS) model. The experimental data and the ERAS model can help to estimate real behaviour of the systems studied.     

Critical behaviour of the order parameters at the SmC* to SmA phase transition in a ferroelectric liquid crystal mixture

Critical behaviour of the order parameters has been investigated in the ferroelectric liquid crystal mixture ZLI‐3654 in a 7.5 µm thick planar cell. The temperature dependence of the primary (tilt angle) and secondary (spontaneous polarisation) order parameters is considered. The critical exponent (β) has been evaluated from the fitting of the temperature dependence of the experimental data for both tilt angle and spontaneous polarisation. Experimental results are compared with the predictions of the de Gennes and Landau models.     

Dynamic Surface Elasticity of Polyelectrolyte/Surfactant Adsorption Films at the Air/Water Interface: Carboxylmethylchitosan and Cetyltrimethylammonium Bromide

The dynamic surface elasticity of the solution of carboxymethylchitosan (CMCH) and cetyltrimethylammonium bromide (C₁₆TAB) was measured as a function of the surfactant concentration and the surface age by the oscillating drop method. The results showed that the surface layer of the CMCH/C₁₆TAB solution transformed from loose to structured with the increase in the surfactant concentration. The surface elasticity versus the surface pressure curve during the adsorption showed different features at different surfactant concentration ranges, which was connected with the structural transformation of the surface layer. Our results show that the measurement of dynamic surface dilational properties is a powerful tool for studying the surface kinetics, which is helpful for dealing non-equilibrium systems in industry.     

Effect of Alcohols on the CMC and Thermodynamic Functions of Anionic Surfactants in DMF/Long‐Chain Alcohol Using Microcalorimetric Method

The critical micelle concentration (CMC) of two kinds of anionic surfactant (including sodium laurate (SLA) and sodium dodecyl sulfate (SDS)) in mixed alcohol and N, N‐dimethyl formamide solvent (DMF) were investigated through measuring power‐time curves by titration microcalorimetry. From data of the lowest point and the area of the power‐time curves, their CMC and ΔH _m ⁰ can be obtained. According to standard thermodynamic equations, ΔG _m ⁰ and ΔS _m ⁰ also can be calculated. For different surfactant, the influences of the carbon number and the concentration of alcohol on the CMC and standard thermodynamic functions are different in DMF polar medium. These thermodynamic functions for micelle formation can be further interpreted.     

Fast polarisation-insensitive optical shutter supported by backflow in dichroic dye-doped dual-frequency liquid crystal

This paper describes a novel implementation of a dual-frequency liquid crystal optical shutter of the guest–host type. The transmissive state of the filter is obtained by applying a low-frequency electric field that brings the dichroic dye in a homeotropic orientation. The light-absorbing state is realised by a twisted planar configuration for which the absorption is quasi-independent of the polarisation. Switching between the two states occurs in about 1 ms and the devices show no scattering for wavelengths inside or outside the absorption band of the dichroic dye. Simulations and experiments reveal how a twisted state is obtained through the backflow phenomenon.     

SELECTIVE SEPARATION OF WATER-ETHANOL MIXTURES THROUGH COPOLYMERIC MEMBRANES: Ⅰ. ACRYLIC ACID AND ACRYLONITRILE COPOLYMER AND ITS IONIZED MEMBRANES

The copolymer of acrylic acid and acrylonitrile has been synthesized and pervaporation properties of the copolymeric membranes have been investigated. In order to elucidate the influence of membrane-permeate interaction on the pervaporation of water-ethanol mixtures and to prepare much improved membranes, the membranes have been treated with alkali metal, alkali earth metal and transition metal salt aqueous solutions. The treated membranes (ionized membranes) exhibited higher separation factors than the untreated membranes. The separation factors of various alkali metal cation membranes decreased in the following order : Li~+>Na~+>K~+, and the permeation rates showed an opposite tendency. The dependence of pervaporation behavior on the copolymer composition ,feed concentration and operating temperature have been studied with both ionized and non-ionized membranes. The apparent activation energies of water and ethanol permeation were calculated.